42291-04-3Relevant articles and documents
General and selective synthesis of primary amines using Ni-based homogeneous catalysts
Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Jiao, Haijun,Murugesan, Kathiravan,Wei, Zhihong
, p. 4332 - 4339 (2020/05/18)
The development of base metal catalysts for industrially relevant amination and hydrogenation reactions by applying abundant and atom economical reagents continues to be important for the cost-effective and sustainable synthesis of amines which represent highly essential chemicals. In particular, the synthesis of primary amines is of central importance because these compounds serve as key precursors and central intermediates to produce value-added fine and bulk chemicals as well as pharmaceuticals, agrochemicals and materials. Here we report a Ni-triphos complex as the first Ni-based homogeneous catalyst for both reductive amination of carbonyl compounds with ammonia and hydrogenation of nitroarenes to prepare all kinds of primary amines. Remarkably, this Ni-complex enabled the synthesis of functionalized and structurally diverse benzylic, heterocyclic and aliphatic linear and branched primary amines as well as aromatic primary amines starting from inexpensive and easily accessible carbonyl compounds (aldehydes and ketones) and nitroarenes using ammonia and molecular hydrogen. This Ni-catalyzed reductive amination methodology has been applied for the amination of more complex pharmaceuticals and steroid derivatives. Detailed DFT computations have been performed for the Ni-triphos based reductive amination reaction, and they revealed that the overall reaction has an inner-sphere mechanism with H2metathesis as the rate-determining step.
Peptide-catalyzed stereoselective conjugate addition reactions generating all-carbon quaternary stereogenic Centers
Kastl, Robert,Wennemers, Helma
supporting information, p. 7228 - 7232 (2013/07/26)
A powerful catalyst: Quaternary stereogenic centers adjacent to tertiary stereocenters were formed with high diastereoselectivities and enantioselectivities in conjugate addition reactions between aldehydes and β,β-disubstituted nitroolefins by using a peptidic catalyst (see scheme). γ-Amino acids and heterocyclic compounds bearing quaternary stereogenic centers are easily accessible from the products. Copyright
PROCESS FOR PREPARING HYDROCINNAMIC ALDEHYDES IN ENANTIOPURE OR ENANTIOMERICALLY ENRICHED FORM
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Page/Page column 26-27, (2010/12/17)
A process is described for preparing hydrocinnamic aldehydes in enantiopure or enantiomerically enriched form of Formula I, in which R is isopropyl or tert-butyl and R' is hydrogen, or R and R' when taken together are a methylenedioxolyl group, comprising the following steps: a) reacting the hydrocinnamic aldehyde of Formula I with the alcohol of Formula Il in enantiopure or enantiomerically enriched form to give the crystallized hemiacetal of Formula III, in which R, R' have the same meaning as Formula I and (*) indicates a stereogenic centre in the absence of a solvent or in one or more aprotic solvents or mixtures thereof with apolar solvents; b) recovering the hydrocinnamic aldehyde of Formula I in enantiopure or enantiomerically enriched form from the crystallized hemiacetal of Formula III and the aldehyde of opposite configuration in enantiopure or enantiomerically enriched form from the hemiacetal crystallization mother liquors. The invention also concerns a process for preparing the alcohol of Formula Il to be introduced into step a).
